WO2012105397A1 - Membrane de séparation pour traitement d'eau et son procédé de production - Google Patents

Membrane de séparation pour traitement d'eau et son procédé de production Download PDF

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WO2012105397A1
WO2012105397A1 PCT/JP2012/051618 JP2012051618W WO2012105397A1 WO 2012105397 A1 WO2012105397 A1 WO 2012105397A1 JP 2012051618 W JP2012051618 W JP 2012051618W WO 2012105397 A1 WO2012105397 A1 WO 2012105397A1
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Prior art keywords
separation membrane
separation
membrane
porous layer
water treatment
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PCT/JP2012/051618
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English (en)
Japanese (ja)
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高木健太朗
小岩雅和
木村将弘
鈴木祐太郎
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東レ株式会社
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Priority to JP2012514245A priority Critical patent/JP5110227B2/ja
Priority to EP12741861.4A priority patent/EP2671628B1/fr
Priority to KR1020137019763A priority patent/KR101909166B1/ko
Priority to CN201280006325.XA priority patent/CN103338846B/zh
Priority to US13/979,096 priority patent/US9527042B2/en
Publication of WO2012105397A1 publication Critical patent/WO2012105397A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1213—Laminated layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/10—Spiral-wound membrane modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions therefor
    • B01D67/00113—Pretreatment of the casting solutions, e.g. thermal treatment or ageing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0013—Casting processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/06—Flat membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1216—Three or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/08—Polysaccharides
    • B01D71/12—Cellulose derivatives
    • B01D71/14—Esters of organic acids
    • B01D71/16—Cellulose acetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/301—Polyvinylchloride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • B01D71/381—Polyvinylalcohol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • B01D71/421—Polyacrylonitrile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/48—Polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0018—Thermally induced processes [TIPS]

Definitions

  • the present invention relates to a separation membrane useful for selective separation of a liquid mixture, and particularly relates to a separation membrane that has both high solute removal properties and high water permeability and can be suitably used for solute removal, and a method for producing the same. .
  • separation membranes have been used in various fields such as water treatment fields such as drinking water production, water purification, and wastewater treatment, and food industry.
  • water treatment fields such as drinking water production, water purification treatment, and wastewater treatment
  • separation membranes are used to remove impurities in water as an alternative to conventional sand filtration and coagulation sedimentation processes.
  • separation membranes are used for the purpose of separating and removing yeasts used for fermentation and concentrating liquids.
  • a separation membrane that selectively separates the components of a liquid mixture is used for industrial water by producing ultrapure water; desalting seawater or brine; removing or separating and recovering components from wastewater in dyeing and electrodeposition coatings. It is used for the construction of closed systems; and the concentration of active ingredients in the food industry.
  • a separation membrane obtained by laminating a separation functional layer made of a crosslinked polyamide obtained by interfacial polycondensation reaction between a polyfunctional amine and a polyfunctional acid derivative (eg, chloride) on a porous membrane is It attracts attention as a separation membrane with high selective separation.
  • the separation membrane used in each field is required to have excellent water permeability from an economical viewpoint. This is because, if the water permeability is excellent, the apparatus becomes compact, so that the equipment cost can be saved, and the membrane replacement cost and the equipment area are advantageous.
  • JP 63-12310 A JP-A-6-47260 JP-A-9-85068 JP 2001-179061 A JP 2005-246207 A JP 2005-186059 A
  • An object of the present invention is to provide a separation membrane that can reduce these burdens and a method for producing the same.
  • the separation membrane of the present invention is a porous membrane obtained by a phase separation method using a solution containing a resin and at least one of N, N-disubstituted isobutyramide and N-monosubstituted isobutyramide. Provide a quality layer.
  • a separation membrane having both high water permeability and high solute removability can be obtained without using a new additive or a modification treatment step after film formation.
  • the chemical cost and waste liquid treatment load can be reduced, and the separation membrane can be provided by a simpler and safer method.
  • the separation membrane can separate components in the raw fluid.
  • the separation membrane may include, for example, (i) a base material, a separation functional layer, and a porous layer disposed between the base material and the separation functional layer.
  • the separation membrane may be composed of (ii) a base material and a porous layer laminated on the base material, or (iii) may be composed of only a porous layer without a base material.
  • the separation membrane of (ii) and (iii) the components in the raw fluid are separated by the porous layer, but this porous layer may have the same configuration as the porous layer in the separation membrane of (i). .
  • the separation membrane of (i) above is suitably employed, for example, as reverse osmosis, forward osmosis, or nanofiltration membrane.
  • the separation membranes (ii) and (iii) are preferably used in sewage treatment and the like, and the components in the raw fluid are separated by the porous layer.
  • FIGS. 1 to 3 show examples of the configurations of the above (i) to (iii) separation membranes, respectively.
  • the separation membrane 1a includes a base material 2a, a separation functional layer 4a, and a porous layer 3a disposed between the base material 2a and the separation functional layer 4a.
  • the separation membrane 1b includes a base material 2b and a porous layer 3b laminated on the base material 2b.
  • the separation membrane 1c includes a porous layer 3c.
  • the porous layers 3b and 3c the same configuration as that of the porous layer 3a can be applied.
  • the base material 2b the structure similar to the base material 2a is applicable.
  • the separation functional layer side surface of the separation membrane is illustrated as a supply side surface 5, and the substrate side surface is illustrated as a permeation side surface 6.
  • the raw fluid is supplied to the surface 5 on the supply side, the raw fluid is separated into a permeated fluid that passes through the separation membrane and moves to the surface 6 side, and a concentrated fluid that remains on the surface 5 side of the separation membrane.
  • the separation membrane of the present invention may have either a flat membrane type or a hollow fiber type according to the quality of the raw fluid and the operation method.
  • a crosslinked polymer is used as the separation functional layer, for example, in terms of pore diameter control and durability.
  • the separation functional layer in the separation membrane of (i) above can contain polyamide as a main component.
  • This separation membrane is suitably used, for example, when drinking water is obtained from seawater, brine, water containing harmful substances, or in the production of industrial ultrapure water.
  • Polyamide is, for example, a polycondensate of a polyfunctional amine and a polyfunctional acid halide.
  • the composition X contains the substance Y as a main component means that the content (concentration) of the substance Y in the composition X is 50% by weight or more, or 60% by weight or more. Or 80% by weight or more, or it may mean that the composition X consists essentially of substance Y.
  • the composition is a concept including a mixture, a composite, a compound, and the like.
  • the separation functional layer constituting the separation membrane of (i) may have an organic-inorganic hybrid structure containing Si element in terms of chemical resistance.
  • the composition of the separation functional layer of the organic-inorganic hybrid structure is not particularly limited.
  • the separation functional layer is A polymer formed by condensation and / or polymerization of only the compound (A), -The polymer formed by superposing
  • the polymer includes a condensate.
  • the compound (A) may be condensed via a hydrolyzable group.
  • Compound B can be polymerized via an ethylenically unsaturated group.
  • the content of the compound (A) is preferably 10% by weight or more, more preferably 20% by weight or more and 50% by weight or less.
  • the content of the compound (B) in the separation functional layer is preferably 90% by weight or less, and more preferably 50% by weight or more and 80% by weight or less.
  • the weight ratio of compound (A) / compound (B) is preferably from 1/9 to 1/1. Within these ranges, a relatively high degree of crosslinking is obtained in the condensation polymer contained in the separation functional layer, so that elution of components from the separation functional layer is suppressed during membrane filtration, resulting in stable filtration performance. Is done.
  • the compound (A), the compound (B) and other compounds may form a compound such as a polymer (including a condensate). Therefore, for example, when discussing the “content ratio of the compound (A) in the separation functional layer”, the compound (A) includes the amount of the component derived from the compound (A) in the polycondensation product. The same applies to the compound (B) and other compounds.
  • the separation functional layer does not have a reactive group having an ethylenically unsaturated group, but may contain a component derived from a silicon compound (C) having a hydrolyzable group. Good. Examples of such a compound (C) will be described later.
  • These compounds (C) may be included as a condensate of only compound (C), or may be included as a condensate of a polymer of compound (A) and compound (B).
  • the thickness of the separation functional layer can conform to the conventional method for measuring the thickness of the separation membrane. For example, after embedding the separation membrane with a resin, an ultrathin section is prepared. After the treatment such as dyeing, it can be measured by observing with a transmission electron microscope. As a main measurement method, when the separation functional layer has a pleat structure, one pleat is measured at intervals of 50 nm in the cross-sectional length direction of the pleat structure located above the porous layer, and the 20 pleats are measured. Can be calculated from the average.
  • the thickness of any separation functional layer is not limited.
  • the thickness of the separation functional layer can be changed depending on the use of the separation membrane, it is preferably 5 nm or more and 3000 nm or less in terms of separation performance and transmission performance, and particularly preferably 5 nm or more and 300 nm or less in terms of transmission performance. preferable.
  • the porous layer gives mechanical strength to the separation membrane.
  • the size and distribution of the pores in the porous layer are not particularly limited, but the porous layer may not have separation performance for components having a small molecular size such as ions.
  • the porous layer may be generally referred to as a “porous membrane”, for example, from the surface on the side where the uniform and fine pores or separation function layer is formed to the other surface. A layer with gradually increasing fine pores.
  • the porous layer has a projected area equivalent circle diameter of the pores measured from the surface using an atomic force microscope or an electron microscope on the surface on the side where the separation functional layer is formed, of 1 nm to 100 nm. Is used. In particular, it preferably has a projected area equivalent circle diameter of 3 nm to 50 nm in terms of interfacial polymerization reactivity and retention of the separation functional membrane.
  • the thickness of the porous layer is not particularly limited, but is preferably in the range of 20 ⁇ m or more and 500 ⁇ m or less, more preferably in the range of 30 ⁇ m or more and 300 ⁇ m or less in terms of the strength of the separation membrane.
  • the material of the porous layer includes polysulfone, polyacrylonitrile, polyamide, polyester, polyvinyl alcohol, polyphenylene sulfide sulfone, polyphenylene sulfone, polyphenylene sulfide, polyether sulfone, polyvinylidene fluoride, cellulose acetate, and polyvinyl chloride, or a mixture thereof. Laminated ones are preferred, and polysulfone (PSf) is preferred as a material having high chemical, mechanical and thermal stability and easy control of the pore diameter.
  • the porous layer can contain these resins as main components.
  • the porous layer is prepared by subjecting a polymer solution dissolved in a solvent containing the above-described porous layer material and at least one of N, N-disubstituted isobutyramide and N-monosubstituted isobutyramide to a phase separation method described later. It is formed by making it porous.
  • N, N-disubstituted isobutyramide and N-monosubstituted isobutyramide are shown in the following formula.
  • R 1 , R 2 and R 3 each include a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a double bond, and 2 to 10 carbon atoms.
  • N, N-disubstituted isobutyramide and N-monosubstituted isobutyramide and details of the solvent of the polymer solution will be described later.
  • the porous layer constituting the separation membranes (ii) and (iii) will be described in detail.
  • the porous layer in the separation membranes (ii) and (iii) is not particularly limited as long as it has a separation function and mechanical strength, and is formed from the same material as the porous layer (i).
  • polyvinyl chloride, polyvinylidene fluoride, polysulfone, polyethersulfone and the like which are easy to form a film by a solution and excellent in physical durability and chemical resistance, are preferable as the main component of the porous layer.
  • the porous layer contains at least one of N, N-disubstituted isobutyramide and N-monosubstituted isobutyramide in the same manner as the porous layer of (i). It is formed by making a polymer solution in which the above-mentioned material is dissolved in the solvent to be contained porous by a phase separation method.
  • the average pore diameter on one surface of the porous layer is preferably twice or more the average pore diameter on the other surface.
  • the thickness of the porous layer is preferably 1 ⁇ m or more and 500 ⁇ m or less, more preferably 5 ⁇ m or more and 200 ⁇ m or less.
  • the thickness of the porous layer is 1 ⁇ m or more, defects such as cracks are unlikely to occur in the porous layer, so that the filtration performance is maintained.
  • the thickness of the porous layer is 500 ⁇ m or less, good transmission performance can be maintained.
  • the form of the porous layer can be observed with a scanning electron microscope, a transmission electron microscope, or an atomic microscope.
  • a scanning electron microscope after separating the porous layer from the substrate (nonwoven fabric) in the separation membranes of (i) and (ii) above, the separation membrane of (iii) is used as it is. Then, this is cut by a freeze cleaving method and used as a sample for cross-sectional observation.
  • This sample is thinly coated with platinum, platinum-palladium, or ruthenium tetrachloride, preferably ruthenium tetrachloride, and observed with a high-resolution field emission scanning electron microscope (UHR-FE-SEM) at an acceleration voltage of 3 kV to 6 kV. .
  • UHR-FE-SEM high-resolution field emission scanning electron microscope
  • Hitachi S-900 electron microscope can be used.
  • the thickness of the porous layer and the projected area equivalent circle diameter are determined from the obtained electron micrograph.
  • the thickness and pore diameter of the porous layer thus obtained are average values.
  • the thickness of a porous layer is an average value of 20-point measurement measured at intervals of 20 ⁇ m in a direction orthogonal to the thickness direction by cross-sectional observation.
  • a hole diameter is an average value of each projected area circle equivalent diameter about 200 holes.
  • the nonwoven fabric which is a fibrous base material may be used at the point which provides moderate mechanical strength, maintaining the separation performance and permeation performance of a separation membrane.
  • nonwoven fabric those made of polyolefin, polyester, cellulose and the like are used, but those made of polyolefin and polyester are preferable from the viewpoint of shape retention.
  • a mixture of a plurality of materials can also be used.
  • a long fiber nonwoven fabric or a short fiber nonwoven fabric can be preferably used.
  • the polymer solution is difficult to penetrate to the back (permeation side) of the substrate, and the porous layer is difficult to peel off.
  • the separation membrane is not uniform due to the fluffing of the base material and that defects such as pinholes are less likely to occur. Therefore, a long fiber nonwoven fabric is particularly preferably used as the substrate.
  • the base material for example, a long fiber nonwoven fabric composed of thermoplastic continuous filaments is used.
  • a long-fiber nonwoven fabric excellent in dimensional stability for the base material because tension is applied in the film forming direction.
  • a polyester long fiber nonwoven fabric is preferable in terms of strength and cost.
  • the fibers in the surface layer on the side opposite to the porous layer in terms of strength are preferably longitudinally oriented compared to the fibers in the surface layer on the porous layer side. According to such a structure, it is possible to more effectively suppress film breakage and the like while maintaining strength. More specifically, the fiber orientation degree in the surface layer opposite to the porous layer of the long-fiber nonwoven fabric is preferably 0 ° or more and 25 ° or less, and the fiber orientation degree in the surface layer on the porous layer side is The orientation degree difference is preferably 10 ° or more and 90 ° or less.
  • the separation membrane manufacturing process includes a heating step.
  • the heating causes a phenomenon that the porous layer or the separation functional layer shrinks.
  • the shrinkage is remarkable in the width direction where no tension is applied in continuous film formation. Since shrinkage causes problems in dimensional stability and the like, a substrate having a small rate of thermal dimensional change is desired.
  • the difference between the fiber orientation degree on the surface layer opposite to the porous layer and the fiber orientation degree on the porous layer side surface layer is 10 ° or more and 90 ° or less, the change in the width direction due to heat may be suppressed. It is possible and preferable.
  • the fiber orientation degree is an index indicating the direction of the fibers of the nonwoven fabric substrate constituting the separation membrane, and the film forming direction when performing continuous film formation is 0 °, that is, the direction perpendicular to the film forming direction, that is, It means the average angle of the fibers constituting the nonwoven fabric substrate when the width direction of the nonwoven fabric substrate is 90 °. Accordingly, the closer to 0 ° the fiber orientation, the longer the orientation, and the closer to 90 °, the lateral orientation.
  • the fiber orientation degree can be measured as follows. Ten small sample samples are taken at random from the nonwoven fabric, and the surface of these samples is photographed at 100 to 1000 times with a scanning electron microscope. In the photographed image, 10 pieces from each sample, 100 fibers in total, when the longitudinal direction (longitudinal direction, film forming direction) of the nonwoven fabric is 0 ° and the width direction (lateral direction) of the nonwoven fabric is 90 ° Measure the angle. The average value of these values is calculated, and the value obtained by rounding off the first decimal place is the fiber orientation degree.
  • each layer such as a base material, a porous layer, and a separation functional layer included in the separation membrane contains 5% by weight or less of additives such as a colorant, an antistatic agent, and a plasticizer in addition to the components described above. It can be contained in a proportion of not more than wt% or not more than 1 wt%.
  • ⁇ Permeation flux> The performance of the separation membrane described above is 0.7 m 3 / m 2 / day or more when seawater having a TDS concentration of 3.5 wt% is permeated at 25 ° C., pH 6.5, and an operating pressure of 5.5 MPa. It is preferable to show a permeation flux. Under the same conditions, the separation membrane preferably exhibits a permeation flux of 1.4 m 3 / m 2 / day or less. A separation membrane exhibiting a permeation flux within these ranges is suitable for water treatment applications.
  • the porous layer is produced by making a N, N-disubstituted isobutyramide or N-monosubstituted isobutyramide solution containing a resin porous by a phase separation method.
  • Non-solvent-induced phase separation is a phenomenon in which a polymer solution is phase-separated into a polymer rich phase and a polymer dilute phase when the non-solvent of the polymer permeates into the polymer solution.
  • the polymer rich phase will be used as the wall of the separation membrane and the polymer dilute phase will be used as the pores of the separation membrane.
  • a good solvent capable of dissolving the polymer at room temperature is used for preparing the polymer solution, and a non-solvent that does not dissolve the polymer is used for coagulation.
  • a polymer non-solvent which is a material for the porous layer, is brought into contact with a polymer solution (membrane forming stock solution) to cause phase separation.
  • a method of delaying non-solvent-induced phase separation by mixing a small amount of a good solvent with a non-solvent, or a method of delaying non-solvent-induced phase separation by using a low-temperature non-solvent also has a desired pore size or It can be employed to provide the number of pores.
  • Thermally induced phase separation is a solution in which a polymer is uniformly dissolved in a solvent at a high temperature, but when cooled to a low temperature, the polymer's ability to dissolve the polymer decreases, so the polymer precipitates and becomes a polymer and a solvent. This is a phenomenon of phase separation.
  • a solvent called a poor solvent that does not dissolve the polymer at room temperature but dissolves the polymer at a high temperature of, for example, 100 ° C. or higher is generally used.
  • it can also be set as a poor solvent by mixing arbitrary non-solvents with a good solvent.
  • phase separation can be used in the present invention.
  • the thermally induced phase separation is suitably used when producing a homogeneous separation membrane.
  • the method for forming the porous layer include a step of dissolving a resin in a solvent, a step of casting the obtained resin solution on a base material, and a step of contacting the resin solution with a non-solvent.
  • a film of a polymer solution containing the above-described resin and solvent is formed on the surface of a substrate (for example, a nonwoven fabric), and the substrate is impregnated with the polymer solution.
  • the substrate having the coating is brought into contact with a coagulation bath containing a non-solvent to coagulate the resin, thereby forming a porous layer on the surface of the substrate.
  • the temperature of the polymer solution is usually preferably selected within the range of 0 ° C. or higher and 120 ° C. or lower from the viewpoint of film forming properties.
  • Resin types are as described above.
  • the concentration of the resin is preferably 5% by weight or more or 8% by weight or more.
  • the concentration of the resin in the polymer solution is preferably 40% by weight or less or 25% by weight or less.
  • concentration of the resin is 5% by weight or more, a porous layer having an appropriate strength is easily obtained, and when it is 40% by weight or less, a separation membrane having an appropriate water permeability is easily obtained.
  • the solvent contained in the polymer solution dissolves the resin.
  • the solvent promotes the formation of the porous layer by acting on the resin and the pore opening agent.
  • the polymer solution contains at least one of the above-described N, N-disubstituted isobutyramide and N-monosubstituted isobutyramide as a solvent. By containing these solvents, a separation membrane having a high porosity of the porous layer and a high water permeability is formed.
  • the N, N-disubstituted isobutyramide is selected from the group consisting of, for example, N, N-dimethylisobutyramide, N, N-diisopropylisobutyramide, and N, N-bis (2-ethylhexyl) isobutyramide. At least one compound is applicable.
  • N-monosubstituted isobutyramide examples include N-methylisobutyramide, N-butylisobutyramide, N-pentylisobutyramide, N-isopropylisobutyramide, N-phenylisobutyramide, N-benzylisobutyramide, N- At least one compound selected from the group consisting of (2-phenylethyl) isobutyramide, N-vinylisobutyramide, and N- (3-butenyl) isobutyramide is applicable. That is, these listed compounds are used alone or as a mixture.
  • N, N-disubstituted isobutyramide, N, N-dimethylisobutyramide (DMIB) having high chemical and thermal stability is particularly preferable.
  • the polymer solution may contain an organic solvent other than N, N-disubstituted isobutyramide and N-monosubstituted isobutyramide as a solvent as long as the effects of the invention are not impaired.
  • an organic solvent that can be mixed with N, N-disubstituted isobutyramide and N-monosubstituted isobutyramide, a solvent having high resin solubility is preferable.
  • solvents examples include N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, methyl ethyl ketone (MEK), etc. Can be used.
  • NMP N-methyl-2-pyrrolidone
  • DMAc N-dimethylacetamide
  • DMF N-dimethylformamide
  • DMSO dimethyl sulfoxide
  • MEK methyl ethyl ketone
  • the concentration (% by weight) of the organic solvent is not specifically limited, but is preferably, for example, 1/9 or more, 1/7 or more, 1/3 or more, 1/1 or more, or 2/1 or more.
  • the mixing ratio is preferably 9/1 or less, 7/1 or less, or 5/1 or less.
  • the concentration of the solvent in the polymer solution is preferably 40% by weight or more, 55% by weight or more, or 60% by weight or more.
  • the concentration of the solvent in the polymer solution is preferably 95% by weight or less, 94.9% by weight or less, or 90% by weight or less.
  • the concentration of the solvent is 40% by weight or more, gelation of the polymer solution is moderately suppressed, and when it is 95% by weight or less, a porous layer having an appropriate strength is easily obtained.
  • the solvent concentration is the sum of the concentrations of N, N-disubstituted isobutyramide and N-monosubstituted isobutyramide and the other organic solvents described above in the polymer solution.
  • a pore-opening agent can also be added to the polymer solution.
  • the pore-opening agent is extracted when immersed in the coagulation bath, and has a function of promoting porosity.
  • the pore-opening agent is preferably one having high solubility in the coagulation bath.
  • inorganic salts such as calcium chloride and calcium carbonate can be used.
  • the pore opening agent may be selected from polyoxyalkylenes such as polyethylene glycol and polypropylene glycol; water-soluble polymers such as polyvinyl alcohol, polyvinyl butyral, and polyacrylic acid; and glycerin.
  • a non-solvent can be added to the polymer solution.
  • the non-solvent is a liquid that does not dissolve the resin.
  • the non-solvent acts to control the pore size by controlling the rate of solidification of the resin.
  • water and alcohols such as methanol and ethanol can be used. Of these, water and methanol are preferable from the viewpoint of ease of wastewater treatment and price.
  • a mixture of a plurality of non-solvents may be used as the non-solvent.
  • the concentration of the resin in the polymer solution is preferably 5% by weight or more and 40% by weight or less, and the concentration of the solvent is 40% by weight or more and 94.9% by weight or less. It is preferable. Moreover, it is preferable that the density
  • the concentration of the pore-opening agent is 0.1% by weight or more, appropriate water permeability can be obtained. Moreover, suitable intensity
  • a non-solvent or a mixed solution containing a non-solvent and a solvent can be used as the coagulation bath.
  • the concentration of the solvent in the coagulation bath is, for example, 5 wt% or more and 95 wt% or less, more specifically 10 wt% or more and 90 wt% or less.
  • the coagulation bath preferably contains at least 5% by weight of non-solvent. When the solvent concentration exceeds 95% by weight (that is, when the non-solvent concentration is less than 5% by weight), the resin is difficult to solidify and a porous layer may not be formed easily.
  • the solvent concentration is less than 5% by weight (that is, if the concentration of the non-solvent is greater than 95% by weight), the solidification rate of the resin becomes excessively high and the pore diameter may become too small. Further, when the concentration of the solvent is 95% by weight or less, the solidification rate of the resin is appropriately controlled, and the porous layer is stably formed.
  • the coagulation rate can be adjusted by the temperature of the coagulation bath.
  • the temperature of the coagulation bath is, for example, 0 to 100 ° C., or 10 to 80 ° C.
  • the method for bringing the substrate having the polymer solution coating into contact with the coagulation bath is not particularly limited.
  • a method of immersing a substrate having a coating in a coagulation bath a method of bringing the coating-side surface of the substrate having a coating into contact with the coagulation bath surface, a glass plate, a metal plate, etc.
  • the side opposite to the film side may be brought into contact with a smooth plate so that the coagulation bath does not go around to the back side, and the substrate having the film may be immersed in the coagulation bath together with the plate.
  • a film of the polymer solution may be formed after the base material is attached to the plate, or the film of the polymer solution may be formed on the base material and then attached to the plate.
  • Formation of the film of the polymer solution on the substrate is performed by applying the polymer solution to the substrate or immersing the substrate in the polymer solution.
  • the polymer solution it may be applied to one side of the substrate or may be applied to both sides.
  • the polymer solution is appropriately impregnated into the porous substrate.
  • the time until the polymer solution is applied on the substrate and then brought into contact with the coagulation bath is preferably in the range of 0.1 second to 5 seconds. If the time until contact with the coagulation bath is within this range, the polymer solution sufficiently penetrates between the fibers of the base material and then solidifies, so that the resin firmly bonds to the base material due to its anchor effect.
  • a PSf resin solution having a predetermined concentration is prepared by dissolving a predetermined amount of PSf in DMIB.
  • This solution is called a polymer solution or a film-forming stock solution.
  • this polymer solution is applied to a substrate made of a non-woven fabric to a substantially constant thickness, and then the surface solvent is removed in the air for a certain period of time, and then PSf is coagulated in the coagulation liquid.
  • the DMIB of the solvent rapidly evaporates and the solidification of PSf rapidly proceeds on the surface portion that comes into contact with the coagulation liquid, and fine communication holes having the portion where the DMIB exists as a nucleus are generated.
  • the volatilization of DMIB and the solidification of PSf proceed more slowly than the surface, so that the DMIB tends to aggregate and form large nuclei, and therefore is generated.
  • the communication hole becomes larger in diameter.
  • the above nucleation conditions gradually change depending on the distance from the surface, so that a layer having a smooth pore size distribution without a clear boundary is formed.
  • the porous layer obtained under such preferable conditions is in the range of 40 ° C. to 100 ° C., preferably in the range of 50 ° C. to 80 ° C., for 1 minute to 10 minutes, more preferably 2 minutes or more.
  • the solute blocking performance and membrane permeability of the separation membrane can be further improved.
  • the separation membrane of (i) the N, N-disubstituted isobutyramide and N-monosubstituted isobutyramide remaining in the porous layer function as an acylation catalyst when forming the separation functional layer, Interfacial polycondensation is promoted.
  • the amount of N, N-disubstituted isobutyramide or N-monosubstituted isobutyramide remaining in the porous layer is measured by the following procedure.
  • the separation membrane of (i) or (ii) is used as a sample for the following operation as it is. This is immersed in 50 g of ethanol for 8 hours. Thereafter, the components extracted into ethanol are measured by gas chromatography. For chromatography, "Agilent (registered trademark)" 1100 Series manufactured by Agilent Technologies can be used.
  • the cast product made of resin is taken out from ethanol and heated at 120 ° C. for 2 hours to be dried. Further, the formed product is cooled to room temperature in a desiccator and then weighed.
  • the separation functional layer in the separation membrane (i) can be produced as follows.
  • the separation functional layer mainly composed of polyamide can be formed by interfacial polycondensation of a polyfunctional amine and a polyfunctional acid halide on the porous layer.
  • the polyfunctional amine has at least two primary amino groups and / or secondary amino groups in one molecule, and at least one of the amino groups is a primary amino group. Says amine.
  • Aromatic polyfunctional amines such as triaminobenzene, 3,5-diaminobenzoic acid, 3-aminobenzylamine and 4-aminobenzylamine, aliphatic amines such as ethylenediamine and propylenediamine, 1,2-diaminocyclohexane, 1 , 4-diaminocyclohexane, 4-aminopiperidine, 4-aminoethylpiperazine, and the like.
  • the polyfunctional amine includes aromatic polyfunctional amines having 2 to 4 primary amino groups and / or secondary amino groups in one molecule. Is preferred.
  • aromatic polyfunctional amine m-phenylenediamine, p-phenylenediamine, and 1,3,5-triaminobenzene are preferably used.
  • m-phenylenediamine hereinafter referred to as m-PDA is more preferable from the standpoint of availability and ease of handling.
  • the polyfunctional amine may be used alone, or two or more polyfunctional amines may be used in combination.
  • the amines exemplified above may be combined with each other, and the above-described amine and an amine having at least two secondary amino groups in one molecule may be combined. Also good.
  • the amine having at least two secondary amino groups in one molecule include piperazine and 1,3-bispiperidylpropane.
  • the polyfunctional acid halide refers to an acid halide having at least two carbonyl halide groups in one molecule.
  • examples of the trifunctional acid halide include trimesic acid chloride, 1,3,5-cyclohexanetricarboxylic acid trichloride, 1,2,4-cyclobutanetricarboxylic acid trichloride, and the like.
  • examples of the bifunctional acid halide include aromatic bifunctional acid halides such as biphenyl dicarboxylic acid dichloride, azobenzene dicarboxylic acid dichloride, terephthalic acid chloride, isophthalic acid chloride, naphthalene dicarboxylic acid chloride, adipoyl chloride, sebacoyl chloride, and the like.
  • Examples thereof include alicyclic bifunctional acid halides such as aliphatic difunctional acid halides, cyclopentane dicarboxylic acid dichloride, cyclohexane dicarboxylic acid dichloride, and tetrahydrofuran dicarboxylic acid dichloride.
  • the polyfunctional acid halide is preferably a polyfunctional acid chloride.
  • the polyfunctional acid halide is preferably a polyfunctional aromatic acid chloride having 2 to 4 carbonyl chloride groups in one molecule.
  • trimesic acid chloride (TMC) is more preferable from the viewpoint of easy availability and easy handling.
  • polyfunctional acid halides may be used alone or in combination of two or more.
  • the polyfunctional acid halide As the polyfunctional acid halide, a bifunctional acid halogen compound and a trifunctional halogen compound can be used.
  • the ratio of the bifunctional acid halogen compound to the trifunctional halogen compound is 0.05 or more in molar ratio (mole of the bifunctional acid halogen compound / mole of the trifunctional acid halogen compound). It is preferably 1.5 or less, and more preferably 0.1 or more and 1.0 or less.
  • the excess amine aqueous solution is removed with an air knife or the like.
  • a polyfunctional acid halide-containing solution is applied, and excess polyfunctional acid halide is removed with an air knife or the like.
  • the monomer may be removed by washing. Further, chemical treatment with chlorine, acid, alkali, nitrous acid, or the like may be performed. Cleaning may be performed after the chemical treatment, or chemical treatment may be performed after the cleaning.
  • An organic solvent is used as a solvent for the solution containing the polyfunctional acid halide.
  • the organic solvent those which are immiscible with water, dissolve polyfunctional acid halides and do not destroy the porous layer are desirable, and are inert to polyfunctional amine compounds and polyfunctional acid halides. Anything is acceptable.
  • Preferred examples include hydrocarbon compounds such as n-hexane, n-octane, and n-decane.
  • the separation functional layer having an organic-inorganic hybrid structure can be obtained by at least one reaction of the condensation of the compound (A) and the polymerization of the compound (A) and the compound (B).
  • the reactive group having an ethylenically unsaturated group is directly bonded to the silicon atom.
  • reactive groups include vinyl groups, allyl groups, methacryloxyethyl groups, methacryloxypropyl groups, acryloxyethyl groups, acryloxypropyl groups, and styryl groups. From the viewpoint of polymerizability, a methacryloxypropyl group, an acryloxypropyl group, and a styryl group are preferable.
  • the compound (A) becomes a polymer by a condensation reaction in which silicon compounds are bonded by a siloxane bond through a process such that a hydrolyzable group directly bonded to a silicon atom is changed to a hydroxyl group.
  • hydrolyzable group examples include functional groups such as alkoxy group, alkenyloxy group, carboxy group, ketoxime group, aminohydroxy group, halogen atom and isocyanate group.
  • the alkoxy group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 2 carbon atoms.
  • the alkenyloxy group preferably has 2 to 10 carbon atoms, more preferably 2 to 4 carbon atoms, and further 3 carbon atoms.
  • the carboxy group is preferably one having 2 to 10 carbon atoms, and more preferably one having 2 carbon atoms, that is, an acetoxy group.
  • ketoxime group examples include a methyl ethyl ketoxime group, a dimethyl ketoxime group, and a diethyl ketoxime group.
  • the aminohydroxy group is one in which an amino group is bonded to a silicon atom via an oxygen atom via oxygen. Examples of such include dimethylaminohydroxy group, diethylaminohydroxy group, and methylethylaminohydroxy group.
  • halogen atom a chlorine atom is preferably used.
  • a silicon compound having a silanol structure in which a part of the hydrolyzable group is hydrolyzed can be used.
  • two or more silicon compounds having a high molecular weight such that a part of the hydrolyzable group is not hydrolyzed, condensed, or crosslinked can be used.
  • the silicon compound (A) is preferably represented by the following general formula (a).
  • R 1 represents a reactive group containing an ethylenically unsaturated group.
  • R 2 represents an alkoxy group, an alkenyloxy group, a carboxy group, a ketoxime group, a halogen atom or an isocyanate group.
  • R 3 represents H or alkyl.
  • M and n are integers satisfying m + n ⁇ 4 and satisfy m ⁇ 1 and n ⁇ 1 In each of R 1 , R 2 and R 3 , two or more functional groups are bonded to a silicon atom. They may be the same or different.
  • R 1 is a reactive group containing an ethylenically unsaturated group, as described above.
  • R 2 is a hydrolyzable group, and these are as described above.
  • the alkyl group as R 3 preferably has 1 to 10 carbon atoms, more preferably 1 to 2 carbon atoms.
  • an alkoxy group is preferably used in forming the separation functional layer because the reaction solution has viscosity.
  • Such silicon compounds include vinyltrimethoxysilane, vinyltriethoxysilane, styryltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropyltriethoxy.
  • Examples include silane and acryloxypropyltrimethoxysilane.
  • a silicon compound (C) that does not have a reactive group having an ethylenically unsaturated group but has a hydrolyzable group can also be used.
  • the compound (A) is defined as “m ⁇ 1” in the general formula (a), whereas the compound (C) is exemplified by a compound in which m is zero in the general formula (a).
  • the Examples of the compound (C) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane.
  • the ethylenically unsaturated group has addition polymerizability.
  • examples of such compounds include ethylene, propylene, methacrylic acid, acrylic acid, styrene, and derivatives thereof.
  • this compound is preferably an alkali-soluble compound having an acid group in order to increase the selective permeability of water and increase the salt rejection when the separation membrane is used for separation of an aqueous solution.
  • Preferred acid structures are carboxylic acid, phosphonic acid, phosphoric acid and sulfonic acid, and these acid structures may exist in any form of acid form, ester compound and metal salt. These compounds having one or more ethylenically unsaturated groups can contain two or more acids, but compounds containing 1 to 2 acid groups are particularly preferred.
  • examples of the compound having a carboxylic acid group include the following. Maleic acid, maleic anhydride, acrylic acid, methacrylic acid, 2- (hydroxymethyl) acrylic acid, 4- (meth) acryloyloxyethyl trimellitic acid and the corresponding anhydride, 10-methacryloyloxydecylmalonic acid, N- ( 2-hydroxy-3-methacryloyloxypropyl) -N-phenylglycine and 4-vinylbenzoic acid.
  • compounds having a phosphonic acid group include vinylphosphonic acid, 4-vinylphenylphosphonic acid, 4-vinylbenzylphosphonic acid, 2-methacryloyloxyethylphosphonic acid.
  • the phosphoric acid ester compounds include 2-methacryloyloxypropyl monohydrogen phosphate, 2-methacryloyloxypropyl dihydrogen phosphate, 2-methacryloyloxyethyl monoester.
  • examples of the compound having a sulfonic acid group include vinylsulfonic acid, 4-vinylphenylsulfonic acid, and 3- (methacrylamide) propylsulfonic acid.
  • a reaction solution containing the compound (A), the compound (B) and a polymerization initiator is used.
  • this reaction liquid By applying this reaction liquid on the porous layer, condensing hydrolyzable groups and polymerizing ethylenically unsaturated groups, these compounds can be made high molecular weight.
  • the cross-linking chain concentrates on the silicon atom, so that the density difference between the periphery of the silicon atom and the portion away from the silicon atom increases. As a result, the pore diameter in the separation functional layer tends to be non-uniform.
  • the compound (B) is copolymerized with the compound (A), so that the crosslinking point by condensation of hydrolyzable groups and the polymerization of ethylenically unsaturated groups Crosslinking points are moderately dispersed. By dispersing the cross-linking points in this way, the pore diameter in the separation membrane is made uniform.
  • a low molecular weight compound having one or more ethylenically unsaturated groups may cause a decrease in membrane performance by elution when using a separation membrane, but because the compound is polymerized in the separation functional layer, Such a decrease in membrane performance can be suppressed.
  • the content of the compound (A) is preferably 10 parts by weight or more, more preferably 20 parts by weight to 50 parts by weight with respect to 100 parts by weight of the solid content contained in the reaction solution.
  • the solid content contained in the reaction liquid is a composite semipermeable membrane obtained by removing the solvent and distilled components such as water and alcohol produced by the condensation reaction from all components contained in the reaction liquid Refers to a component finally contained as a separation functional layer.
  • the amount of the compound (A) is sufficient, a sufficient degree of crosslinking can be obtained, and the possibility of occurrence of problems such as elution of the components of the separation functional layer during membrane filtration and degradation of the separation performance is reduced.
  • the content of the compound (B) is preferably 90 parts by weight or less, more preferably 50 parts by weight to 80 parts by weight with respect to 100 parts by weight of the solid content contained in the reaction solution.
  • the resulting separation functional layer has a high degree of crosslinking, and therefore membrane filtration can be performed stably without the separation functional layer eluting.
  • a step of applying a reaction solution containing the compound (A) and the compound (B), a step of removing the solvent, a step of polymerizing ethylenically unsaturated groups, a step of condensing a hydrolyzable group are exemplified in this order.
  • the step of polymerizing the ethylenically unsaturated group it may be included that the hydrolyzable group is condensed at the same time.
  • reaction solution containing the compound (A) and the compound (B) is brought into contact with the porous layer.
  • a reaction solution is usually a solution containing a solvent, but such a solvent does not destroy the porous layer and dissolves the compound (A), the compound (B), and a polymerization initiator added as necessary. If it is a thing, it will not specifically limit.
  • 1 to 10-fold molar amount of water preferably 1 to 5-fold molar amount of water, together with an inorganic acid or an organic acid, to this reaction solution, relative to the number of moles of compound (A), compound (A ) Can be promoted.
  • the solvent for the reaction solution is preferably water, an alcohol-based organic solvent, an ether-based organic solvent, a ketone-based organic solvent, or a mixture thereof.
  • an alcohol organic solvent methanol, ethoxymethanol, ethanol, propanol, butanol, amyl alcohol, cyclohexanol, methylcyclohexanol, ethylene glycol monomethyl ether (2-methoxyethanol), ethylene glycol monoacetate, diethylene glycol monomethyl ether
  • Examples include diethylene glycol monoacetate, propylene glycol monoethyl ether, propylene glycol monoacetate, dipropylene glycol monoethyl ether, and methoxybutanol.
  • ether organic solvents include methylal, diethyl ether, dipropyl ether, dibutyl ether, diamyl ether, diethyl acetal, dihexyl ether, trioxane, dioxane and the like.
  • ketone organic solvents include acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl cyclohexyl ketone, diethyl ketone, ethyl butyl ketone, trimethylnonanone, acetonitrile acetone, dimethyl oxide, phorone, cyclohexanone, dye Acetone alcohol etc. are mentioned.
  • the amount of the solvent added may be 50 to 99 parts by weight, or 80 to 99 parts by weight with respect to 100 parts by weight of the solid content contained in the reaction solution. If the amount of the solvent added is too large, defects tend to occur in the membrane, and if it is too small, the water permeability of the resulting separation membrane tends to be low.
  • the contact between the porous layer and the reaction solution is preferably performed uniformly and continuously on the porous layer.
  • a method of coating the reaction solution on the porous layer using a coating apparatus such as a spin coater, a wire bar, a flow coater, a die coater, a roll coater, or a spray.
  • a coating apparatus such as a spin coater, a wire bar, a flow coater, a die coater, a roll coater, or a spray.
  • the method of immersing a porous layer in a reaction liquid can be mentioned.
  • the contact time between the porous layer and the reaction solution is preferably in the range of 0.5 to 10 minutes, and more preferably in the range of 1 to 3 minutes.
  • By sufficiently draining the liquid it is possible to prevent the remaining portion of the liquid droplet from becoming a film defect after the film is formed and deteriorating the film performance.
  • a method for draining liquid a method is used in which the porous layer after contact with the reaction liquid is vertically gripped and the excess reaction liquid is allowed to flow down naturally, or air such as nitrogen is blown from an air nozzle to forcibly drain the liquid. (That is, an air knife) can be used.
  • the membrane surface can be dried to remove a part of the solvent in the reaction solution.
  • the step of condensing the hydrolyzable group of silicon is carried out by heat treatment after bringing the reaction solution into contact with the porous layer.
  • the heating temperature at this time is required to be lower than the temperature at which the porous layer melts and the performance as a separation membrane is lowered.
  • the reaction temperature is preferably 150 ° C. or lower, and more preferably 100 ° C. or lower. If the reaction temperature is 0 ° C. or higher, the hydrolysis and condensation reaction proceed rapidly, and if it is 150 ° C. or lower, the hydrolysis and condensation reaction are easily controlled. Further, by adding a catalyst that promotes hydrolysis or condensation, the reaction can proceed even at a lower temperature. Furthermore, the condensation reaction can be appropriately performed by selecting the heating condition and the humidity condition so that the separation functional layer has pores.
  • the polymerization method of the ethylenically unsaturated group of the compound (A) and the compound (B) having an ethylenically unsaturated group can be carried out by heat treatment, electromagnetic wave irradiation, electron beam irradiation, or plasma irradiation.
  • the electromagnetic wave includes infrared rays, ultraviolet rays, X-rays, ⁇ rays and the like.
  • the polymerization method may be appropriately selected as appropriate, but polymerization by electromagnetic wave irradiation is preferred from the viewpoint of running cost, productivity and the like.
  • electromagnetic waves infrared irradiation and ultraviolet irradiation are more preferable from the viewpoint of simplicity.
  • these light sources do not need to selectively generate only light in this wavelength range, and any light source containing electromagnetic waves in these wavelength ranges may be used.
  • the intensity of these electromagnetic waves is higher than electromagnetic waves in other wavelength regions.
  • Electromagnetic waves can be generated from halogen lamps, xenon lamps, UV lamps, excimer lamps, metal halide lamps, rare gas fluorescent lamps, mercury lamps, and the like.
  • the energy of the electromagnetic wave is not particularly limited as long as it can be polymerized, but particularly high-efficiency, low-wavelength ultraviolet rays have a high film-forming property.
  • Such ultraviolet rays can be generated by a low-pressure mercury lamp or an excimer laser lamp.
  • the thickness and form of the separation functional layer may vary greatly depending on the respective polymerization conditions. In the case of polymerization using electromagnetic waves, the thickness and form of the separation functional layer may vary greatly depending on the wavelength and intensity of the electromagnetic waves, the distance to the irradiated object, and the treatment time. Therefore, these conditions need to be optimized as appropriate.
  • the polymerization initiator and the polymerization accelerator are not particularly limited, and are appropriately selected according to the structure of the compound to be used, the polymerization technique, and the like.
  • the polymerization initiator is exemplified below.
  • an initiator for polymerization by electromagnetic waves benzoin ether, dialkylbenzyl ketal, dialkoxyacetophenone, acylphosphine oxide or bisacylphosphine oxide, ⁇ -diketone (for example, 9,10-phenanthrenequinone), diacetylquinone, furylquinone, anisylquinone, Examples are 4,4'-dichlorobenzylquinone and 4,4'-dialkoxybenzylquinone, and camphorquinone.
  • Initiators for thermal polymerization include azo compounds (eg, 2,2′-azobis (isobutyronitrile) (AIBN) or azobis- (4-cyanovaleric acid)), or peroxides (eg, peroxide) Dibenzoyl, dilauroyl peroxide, tert-butyl peroctanoate, tert-butyl perbenzoate or di- (tert-butyl) peroxide), aromatic diazonium salts, bissulfonium salts, aromatic iodonium salts, aromatic sulfonium salts, Examples include potassium persulfate, ammonium persulfate, alkyl lithium, cumyl potassium, sodium naphthalene, and distyryl dianion. Of these, benzopinacol and 2,2'-dialkylbenzopinacol are particularly preferred as initiators for radical polymerization.
  • benzopinacol and 2,2'-dialkylbenzopinacol
  • Peroxides and ⁇ -diketones are preferably used in combination with aromatic amines to accelerate initiation. This combination is also called a redox system. Examples of such systems include benzoyl peroxide or camphorquinone and amines (eg, N, N-dimethyl-p-toluidine, N, N-dihydroxyethyl-p-toluidine, ethyl p-dimethyl-aminobenzoate). Ester or a derivative thereof). Furthermore, a system containing a peroxide in combination with ascorbic acid, barbiturate or sulfinic acid as a reducing agent is also preferred.
  • the step of increasing the molecular weight of the silane coupling agent and the compound having one or more ethylenically unsaturated groups may be performed before the polycondensation step of the silane coupling agent, or after You can go. Moreover, you may carry out simultaneously.
  • the thus obtained separation membrane having an organic-inorganic hybrid structure can be used as it is, but before use, it is preferable to hydrophilize the surface of the membrane with, for example, an alcohol-containing aqueous solution or an alkaline aqueous solution.
  • the separation membrane described above can be used as a component of the separation membrane element.
  • the separation membrane element obtains a permeated fluid from the other surface by supplying the raw fluid to one surface of the separation membrane.
  • the separation membrane element includes a large number of bundled separation membranes so that a large membrane area can be secured and a large amount of permeating fluid can be obtained per unit element.
  • Various shapes such as a spiral type, a hollow fiber type, a plate-and-frame type, a rotating flat membrane type, and a flat membrane integrated type can be adopted for the separation membrane element in accordance with the application and purpose.
  • FIG. 4 is a partially developed perspective view schematically showing the configuration of the spiral separation membrane element.
  • a polymer net 8 is used as a supply-side channel material that forms a supply-side channel.
  • a fabric member called a tricot 9 having a smaller interval than the supply side channel material is used for the purpose of preventing the separation membrane 1d from falling and forming a permeate side channel.
  • An envelope-like membrane 10 is formed by the separation membrane 1d that is superposed on both surfaces of the permeate-side channel material and adhered in an envelope shape.
  • the inside of the envelope membrane 10 constitutes a permeate fluid flow path, and the envelope membrane 10 alternately laminated with the net 8 is bonded to a predetermined portion on the opening side to the outer peripheral surface of the perforated water collecting pipe 11 to form a spiral. Wrapped in a shape.
  • the fluid separation by the spiral separation membrane element 7 will be described.
  • the raw fluid 13 is supplied to one end face in a state where the separation membrane element 7 is disposed in a pressure vessel (not shown).
  • the supplied raw fluid 13 is separated into a permeating fluid 14 that permeates the separation membrane 1d and a concentrated fluid 15 that contains a substance that does not permeate.
  • the permeating fluid 14 reaches the perforated water collecting pipe 12 by passing through the hole 11.
  • the permeated fluid 14 that has passed through the perforated water collecting pipe 12 is discharged out of the separation membrane element 7 through the permeated fluid outlet 16.
  • the concentrated fluid 15 moves through the separation membrane element 7 by flowing between the separation membranes, and is finally discharged from the concentrated fluid outlet 17 to the outside of the separation membrane element 7.
  • the above-described separation membrane, its elements, and modules can be combined with a pump that supplies raw water to them, a device that pretreats the raw water, and the like to form a fluid separation device.
  • a separation device By using this separation device, permeated water such as drinking water and concentrated water that has not permeated through the membrane can be separated from the raw water, and water suitable for the purpose can be obtained.
  • the pressure is preferably from 0.1 MPa to 10 MPa.
  • the salt desalting rate decreases, but as the feed water temperature decreases, the membrane permeation flux also decreases.
  • the raw fluid pH becomes high, in the case of high salt concentration supply water such as seawater, scales such as magnesium may occur, and there is a concern about membrane deterioration due to high pH operation. Is preferred.
  • the fluid to be treated by the separation membrane is not particularly limited, but when used for water treatment, examples of the supply water include liquid mixtures such as seawater, brine, and wastewater. Specifically, these liquid mixtures contain 0.05 wt% or more and 10 wt% or less of total dissolved solids (Total Dissolved Solids: TDS). According to the definition, the solution filtered with a 0.45 micron filter can be calculated from the weight of the residue by evaporating at a temperature of 39.5 to 40.5 ° C, but more simply converted from practical salt (S) To do.
  • TDS Total Dissolved Solids
  • Seawater having a TDS concentration of 3.5% by weight adjusted to a temperature of 25 ° C. and a pH of 6.5 was supplied to the separation membrane as a raw fluid (that is, supply water) at an operating pressure of 5.5 MPa.
  • the permeated water obtained by supplying water is separated into permeate and concentrate, as desalination of the separation membrane, desalination amount permeability per day at the membrane surface 1 square meter (cubic meters) (m 3 / m 2 / day).
  • the fiber-reinforced porous membrane was cut into a circle with a diameter of 50 mm.
  • the cut fiber-reinforced porous membrane was set in a cylindrical filter holder, and distilled water was preliminarily permeated at 25 ° C. at a head height of 1 m (9.8 kPa) for 5 minutes. Subsequently, distilled water was permeated under the same conditions, and the permeated water was collected for 3 minutes.
  • the amount of permeated water thus obtained was converted to a value per unit time and effective membrane area, and further converted to pressure, thereby calculating water permeation performance (m 3 / m 2 / s / Pa) as water permeability.
  • solute rejection of fiber-reinforced porous membrane (polystyrene fine particle rejection)
  • the solute rejection was measured as follows. In the following, in particular, the rejection rate against polystyrene fine particles was measured as the solute rejection rate.
  • the stock solution for evaluation was prepared by dispersing polystyrene fine particles (manufactured by Magshere Co., Ltd., average particle size 0.083 ⁇ m, nominal particle size 0.032 ⁇ m) in distilled water to a concentration of 20 ppm.
  • a fiber-reinforced porous membrane cut into a circle with a diameter of 4.3 cm was set in a stirring cell (VHP-43K, manufactured by Advantech Co., Ltd.), and 10 ml of the evaluation stock solution of 50 ml at an evaluation pressure of 100 kPa and a stirring speed of 700 rpm. Was filtered. 3 ml of the permeate thus obtained and the evaluation stock solution remaining in the stirring cell were recovered. It calculated
  • Fine particle rejection (%) ⁇ 1 ⁇ (absorbance of permeated water) / (absorbance of supplied water) ⁇ ⁇ 100
  • a spectrophotometer (U-3200) manufactured by Hitachi, Ltd. was used for the absorbance measurement.
  • Example 1 a Production of Fiber Reinforced Porous Membrane PSf (manufactured by Solvay Advanced Polymers, Udel (registered trademark) P3500) was used as a resin constituting the porous layer. Further, DMIB was used as a solvent for the polymer solution. These were sufficiently stirred at 95 ° C. to prepare a polymer solution (film forming stock solution) composed of 15.0 wt% PSf and 85.0 wt% DMIB.
  • a polymer solution film forming stock solution
  • a nonwoven fabric composed of polyester long fibers (yarn diameter: 1 dtex, thickness: about 90 ⁇ m, air permeability: 1 cc / cm 2 / sec, fibers on the porous layer side surface layer)
  • the fiber was cast at a thickness of 180 ⁇ m at room temperature (25 ° C.) on an orientation degree of 40 ° and a fiber orientation degree on the surface layer opposite to the porous layer: 20 °.
  • it is immersed in pure water, left in pure water for 20 seconds, and then washed with hot water at 75 ° C. for 2 minutes, whereby a fiber-reinforced porous membrane having a substrate and a porous membrane (thickness) 140 ⁇ m).
  • Table 1 shows the measurement results together with other examples and comparative examples.
  • Example 2 A fiber-reinforced porous membrane was produced in the same manner as in Example 1 except that the casting temperature of the polymer solution in the formation of the porous layer was changed to 40 ° C.
  • a separation functional layer was formed on the fiber reinforced porous membrane in the same manner as in Example 1 to produce a separation membrane.
  • Table 1 shows the performance of each film.
  • Example 3 In the polymer solution used for forming the porous layer, fiber reinforced porous material was used in the same manner as in Example 1 except that polyethersulfone (PES: Ultrason (registered trademark) E6020, manufactured by BASF) was used in addition to PSf as a resin. A membrane was prepared. As shown in Table 1, the concentration of Psf in the polymer solution was 5.0% by weight, and the concentration of PES was 10.0% by weight.
  • PES Ultrason (registered trademark) E6020, manufactured by BASF
  • a separation functional layer was formed on the fiber reinforced porous membrane in the same manner as in Example 1 to produce a separation membrane.
  • Table 1 shows the performance of each film.
  • Example 4 fiber-reinforced porous membranes were prepared in the same manner as in Example 1 except that the solvent of the polymer solution used for forming the porous layer was changed to a mixed solvent of DMIB and DMF. Moreover, the separation membrane was produced by forming a separation functional layer on the obtained fiber-reinforced porous membrane in the same manner as in Example 1.
  • Table 1 shows the concentration of each solvent in the polymer solutions of Examples 4 to 6, the performance of the obtained fiber-reinforced porous membrane, and the performance of the separation membrane having the separation functional layer.
  • Example 7 a fiber-reinforced porous membrane was prepared in the same manner as in Example 1 except that the solvent of the polymer solution used for forming the porous layer was changed to a mixed solvent of DMIB and NMP. Table 1 shows the concentration of each solvent in the polymer solution.
  • a separation functional layer was formed on the fiber reinforced porous membrane in the same manner as in Example 1 to produce a separation membrane.
  • Table 1 shows the performance of each film.
  • Example 8 a fiber-reinforced porous membrane was produced in the same manner as in Example 1 except that the solvent of the polymer solution used for forming the porous layer was changed to a mixed solvent of DMIB and DMSO. Table 1 shows the concentration of each solvent in the polymer solution.
  • a separation functional layer was formed on the fiber reinforced porous membrane in the same manner as in Example 1 to produce a separation membrane.
  • Table 1 shows the performance of each film.
  • Example 9 a fiber-reinforced porous membrane was produced in the same manner as in Example 1 except that the solvent of the polymer solution used for forming the porous layer was changed to a mixed solvent of DMIB and DMAc. Table 1 shows the concentration of each solvent in the polymer solution.
  • a separation functional layer was formed on the fiber reinforced porous membrane in the same manner as in Example 1 to produce a separation membrane.
  • Table 1 shows the performance of each film.
  • Example 10 a fiber-reinforced porous membrane was produced in the same manner as in Example 1 except that the solvent of the polymer solution used for forming the porous layer was changed to a mixed solvent of DMIB and NIB. Table 1 shows the concentration of each solvent in the polymer solution.
  • a separation functional layer was formed on the fiber reinforced porous membrane in the same manner as in Example 1 to produce a separation membrane.
  • Table 1 shows the performance of each film.
  • Example 11 In Example 11, a fiber-reinforced porous membrane was produced in the same manner as in Example 1 except that the solvent in the polymer solution used for forming the porous layer was changed to NIB.
  • a separation functional layer was formed on the fiber reinforced porous membrane in the same manner as in Example 1 to produce a separation membrane.
  • Table 1 shows the performance of each film.
  • Example 12 a fiber-reinforced porous membrane was produced in the same manner as in Example 1 except that the solvent in the polymer solution used for forming the porous layer was changed to a mixed solvent of NIB and DMF. Table 1 shows the concentration of each solvent in the polymer solution.
  • a separation functional layer was formed on the fiber reinforced porous membrane in the same manner as in Example 1 to produce a separation membrane.
  • Table 1 shows the performance of each film.
  • Example 13 and 14 a fiber-reinforced porous membrane was produced in the same manner as in Example 1 except that the base material was changed.
  • Example 13 a non-woven fabric obtained from a long-fiber non-woven fabric by a paper making method was used.
  • Example 14 a long fiber nonwoven fabric having a fiber orientation degree of 20 ° on the porous layer side surface layer and a fiber orientation degree of 40 ° on the surface layer opposite to the porous layer was used.
  • a separation functional layer was formed on the fiber reinforced porous membrane in the same manner as in Example 1 to produce a separation membrane.
  • Table 1 shows the performance of each film.
  • Example 15 A separation membrane was produced in the same manner as in Example 1 except that the following conditions were changed with respect to the formation of the separation functional layer.
  • TMC concentration was changed to 0.120% by weight, and the TPC concentration was changed to 0.010% by weight.
  • the cleaning temperature of the separation membrane after the separation functional layer was formed was changed to 40 ° C.
  • Table 1 shows the performance of each film.
  • Example 15 since the fiber-reinforced porous membrane obtained under the same conditions as in Example 1 was used, the description of the performance of the fiber-reinforced porous membrane was omitted in the table.
  • Polyvinylidene fluoride (PVDF: manufactured by Kureha Chemical Industry Co., Ltd., KF polymer # 1100) was used as a resin constituting the separation membrane. Further, a mixed solvent of DMIB and DMF was used as a solvent for the polymer solution. Polyethylene glycol (PEG) having a molecular weight of 10,000 was used as a pore-opening agent, and water was used as a non-solvent. These were sufficiently stirred at 95 ° C. to prepare a polymer solution composed of PVDF 18.0 wt%, DMIB 25.0 wt%, DMF 50.0 wt%, PEG 5.0 wt%, and water 2.0 wt%.
  • PVDF Polyvinylidene fluoride
  • a nonwoven fabric composed of polyester long fibers (yarn diameter: 3 dtex, thickness: about 160 ⁇ m, air permeability: 4.3 cc / cm 2 / sec, density 0.4 g / cm 3 )
  • a room temperature 25 ° C.
  • it is immersed in pure water, left in pure water for 20 seconds, and then washed with hot water at 90 ° C. for 2 minutes, whereby a fiber-reinforced porous membrane having a substrate and a porous membrane (thickness) 280 ⁇ m).
  • Example 17 In Example 17, a separation membrane was prepared in the same manner as in Example 16 except that the concentrations of DMIB and DMF were changed in the solvent in the polymer solution used for forming the porous layer.
  • PVDF manufactured by Kureha Chemical Co., Ltd., KF polymer # 1100
  • a mixed solvent of DMIB and DMF was used as a solvent.
  • Table 1 shows the performance of the obtained separation membrane.
  • Comparative Examples 1 to 4 fiber reinforced porous membranes were prepared in the same manner as in Example 1 except that the solvent of the polymer solution used for forming the porous layer was changed to DMF, NMP, DMSO, and DMAc, respectively. Moreover, the separation membrane was produced by forming a separation functional layer on the obtained fiber-reinforced porous membrane in the same manner as in Example 1.
  • Table 1 shows the performance of the fiber-reinforced porous membrane obtained in Comparative Examples 1 to 4 and the performance of the separation membrane having the separation functional layer. However, in Comparative Example 3, because the separation functional layer was peeled from the porous layer, the performance of the separation membrane having the separation functional layer could not be measured.
  • Example 5 The polymer solution used for forming the porous layer was the same as in Example 1 except that the resin was changed to 5.0 wt% PSf and 10.0 wt% PES, and the solvent was changed to 85.0 wt% DMF. A fiber-reinforced porous membrane was prepared.
  • a separation functional layer was formed on the fiber reinforced porous membrane in the same manner as in Example 1 to produce a separation membrane.
  • Table 1 shows the performance of each film.
  • Comparative Example 6 A fiber-reinforced porous membrane was produced in the same manner as in Comparative Example 1 except that the following conditions were changed with respect to the formation of the separation functional layer, and a separation membrane further comprising a separation functional layer was produced.
  • the TMC concentration was changed to 0.120% by weight, and the TPC concentration was changed to 0.010% by weight.
  • the cleaning temperature of the separation membrane after the separation functional layer was formed was changed to 40 ° C.
  • Table 1 shows the performance of each film.
  • surface was abbreviate
  • Comparative Example 7 a fiber-reinforced porous membrane was produced in the same manner as in Example 16 except that the solvent was changed to DMF in the polymer solution used for forming the porous layer.
  • a separation functional layer was formed on the fiber reinforced porous membrane in the same manner as in Example 1 to produce a separation membrane.
  • Table 1 shows the performance of each film.
  • Table 1 shows the performance of each film.
  • DMIB / DMF and “70/15 (wt%)” indicate that a mixed solvent of DMIB and DMF was used, and that the DMIB concentration in the polymer solution was 70 wt. %, Meaning that the DMF concentration was 15% by weight.
  • the resin For example, in Example 3, the PSf concentration in the polymer solution was 5% by weight, and the PES concentration was 10% by weight.
  • DMIB N, N-dimethylisobutyramide
  • DMF N, N-dimethylformamide
  • NMP N-methyl-2-pyrrolidone
  • DMSO Dimethyl sulfoxide
  • DMAc N, N-dimethylacetamide
  • NIB N-methylisobutyramide
  • PSf Polysulfone PES: Polyethersulfone PVDF: Polyvinylidene fluoride
  • PSt Polystyrene
  • the separation membrane of the present invention can obtain a separation membrane having both high water permeability and high solute removal without using a new additive or a modification process step after film formation. It can be suitably used for sewage treatment and drinking water production.

Abstract

L'invention porte sur une membrane de séparation pour le traitement d'eau, comprenant une couche poreuse qui est obtenue par un procédé de séparation de phases utilisant une solution contenant une résine et un isobutylamide N,N-disubstitué et/ou un isobutylamide N-monosubstitué.
PCT/JP2012/051618 2011-01-31 2012-01-26 Membrane de séparation pour traitement d'eau et son procédé de production WO2012105397A1 (fr)

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JP2012514245A JP5110227B2 (ja) 2011-01-31 2012-01-26 水処理用分離膜およびその製造方法
EP12741861.4A EP2671628B1 (fr) 2011-01-31 2012-01-26 Procédé de production de membrane de séparation pour traitement d'eau
KR1020137019763A KR101909166B1 (ko) 2011-01-31 2012-01-26 수처리용 분리막 및 그 제조 방법
CN201280006325.XA CN103338846B (zh) 2011-01-31 2012-01-26 水处理用分离膜及其制造方法
US13/979,096 US9527042B2 (en) 2011-01-31 2012-01-26 Separation membrane for water treatment and production method for same

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CN107913604B (zh) * 2017-09-14 2020-12-22 中南大学 一种pvdf/pvdf-hfp中空纤维膜的制备方法
JP7226708B2 (ja) 2018-01-30 2023-02-21 日東電工株式会社 複合半透膜及びその製造方法
CN113522048B (zh) * 2021-07-13 2022-07-01 陕西科技大学 一种基于肟氨酯键的油水分离膜、制备方法及其应用
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JP5110227B2 (ja) 2012-12-26
KR101909166B1 (ko) 2018-10-17
CN103338846A (zh) 2013-10-02
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